US4619790A - Manufacture of higher alkylcarboxylic acids - Google Patents
Manufacture of higher alkylcarboxylic acids Download PDFInfo
- Publication number
- US4619790A US4619790A US05/874,316 US87431678A US4619790A US 4619790 A US4619790 A US 4619790A US 87431678 A US87431678 A US 87431678A US 4619790 A US4619790 A US 4619790A
- Authority
- US
- United States
- Prior art keywords
- olefin
- cobalt
- manufacture
- olefins
- propylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
Definitions
- the present invention relates to an improved process for the manufacture of alkylcarboxylic acids (where alkyl is of 6 to 20 carbon atoms), by hydrocarboxylating the corresponding olefins of 6 to 20 carbon atoms.
- the hydrocarboxylation of olefins, in accordance with the following equation ##STR1## R alkyl is a conventional process for the manufacture of alkylcarboxylic acids.
- the above conventional syntheses relate to the use of cobalt carbonyl compounds as catalysts, since the nickel carbonyl compounds and noble metal carbonyl compounds which are also conventionally used for carbonylations give even less advantageous results when used for the hydrocarboxylation of the higher olefins, either in respect of the yield or because of the technical difficulties resulting from the volatility of nickel carbonyl or because of losses of noble metals, eg. palladium or rhodium.
- alkylcarboxylic acids where alkyl is of 6 to 20 carbon atoms
- alkylcarboxylic acids where alkyl is of 6 to 20 carbon atoms
- hydrocarboxylating the corresponding olefins by means of cobalt carbonyl compounds in the presence of a solvent, in higher absolute yield and with a higher space-time yield if from 0.2 to 3 kg of N-methylpyrrolidone, per kg of the olefin, is used as the solvent.
- Suitable starting compounds include both unbranched and branched olefins with a terminal or non-terminal double bond. According to the conventional rules, these olefins merely differ in reactivity, which generally decreases with increasing degree of branching and with increasing steric screening of the double bond. However, the lower reactivity of such olefins can be substantially counterbalanced by using more severe reaction conditions. Linear ⁇ -olefins react particularly easily and, as a result of the presence of N-methylpyrrolidone in accordance with the invention, predominantly give the N-alkylcarboxylic acids, which in the main are the desired products.
- the process is also of particular importance for hydrocarboxylating propylene and butylene oligomers, e.g., trimeric propylene, tetrameric propylene and diisobutylene. These are frequently isomer mixtures, so that the products obtained are also mixtures of isomeric carboxylic acids.
- preferred olefins are linear olefins and mixtures of olefins of 8 to 15 carbon atoms as obtained on cracking paraffin.
- the process is carried out under the conventional reaction conditions for hydrocarboxylation, i.e., under a CO pressure of from 100 to 1,000 bars and at a temperature of from 150° to 220° C.
- a CO pressure of from 100 to 1,000 bars and at a temperature of from 150° to 220° C.
- from 1 to 2 moles of water and from 0.01 to 0.1 mole equivalent (expressed as cobalt) of the cobalt catalyst are used per mole of olefin.
- the cobalt can be employed in the form of dicobalt-octacarbonyl, but cobalt salts, e.g.
- cobalt acetate or cobalt palmitate in general fulfil the same purpose, since the active carbonyl complexes are formed in situ under the reaction conditions.
- the cobalt salts (cobalt soaps) of the carboxylic acids formed during the process are particularly suitable.
- the preferred amount of N-methylpyrrolidone is from 0.5 to 1.5 kg/kg of olefin.
- the process can be carried out batchwise but as a rule a continuous method is preferred, for economic and technological reasons.
- the procedure followed is, in general, to charge the reactor with the solution of the dicobalt-octacarbonyl in the olefin, and with aqueous N-methylpyrrolidone. If the cobalt is employed in the form of its salts, these can also be added to the aqueous solvent phase.
- air is passed through the reaction mixture, whereby the cobalt compound is reconverted to the Co-II form.
- a different oxidizing agent preferably hydrogen peroxide, can be used.
- the mixture is then subjected to fractional distillation. N-Methylpyrrolidone and unconverted olefin are recycled, as is the high-boiling residue which contains the cobalt and which, before introduction into the reactor, is advantageously dissolved in the olefin.
- the desired carboxylic acids are obtained in yields of from about 75 to 90%. From about 5 to 20% are accounted for by unconverted olefin and the remainder is in the form of by-products, including, above all, the paraffin corresponding to the olefin.
- the economics of the process taking into account the yields, by-products and process costs, are throughout from about 10 to 50% better.
- the higher alkylcarboxylic acids are in the main used for the manufacture of plasticizers, dryers and corrosion protection agents.
- the yield of 3,5,5-trimethylhexanoic acid was 78%. 15% of the olefin remained unchanged, 5% were hydrogenated to the paraffin and the remainder comprised aldehydes, esters and other by-products.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2709438A DE2709438C3 (de) | 1977-03-04 | 1977-03-04 | Verfahren zur Herstellung von C6. bis C20 Alkylcarbonsäuren |
DE2709438 | 1977-03-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
US4619790A true US4619790A (en) | 1986-10-28 |
Family
ID=6002766
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/874,316 Expired - Lifetime US4619790A (en) | 1977-03-04 | 1978-02-01 | Manufacture of higher alkylcarboxylic acids |
Country Status (7)
Country | Link |
---|---|
US (1) | US4619790A (fr) |
JP (1) | JPS6058900B2 (fr) |
AT (1) | AT356641B (fr) |
BE (1) | BE864265A (fr) |
DE (1) | DE2709438C3 (fr) |
FR (1) | FR2382425A1 (fr) |
GB (1) | GB1595037A (fr) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4665213A (en) * | 1985-08-29 | 1987-05-12 | The British Petroleum Company P.L.C. | Process for the production of esters |
US20040238785A1 (en) * | 2000-12-22 | 2004-12-02 | Eddy Van Driessche | Ester-containing fluid compositions |
KR100763216B1 (ko) | 2001-02-13 | 2007-10-08 | 옥세노 올레핀케미 게엠베하 | 고순도 디이소부텐의 제조방법 |
CN109942399A (zh) * | 2017-12-21 | 2019-06-28 | 赢创德固赛有限公司 | 将二异丁烯直接转化为羧酸的方法 |
CN109942398A (zh) * | 2017-12-21 | 2019-06-28 | 赢创德固赛有限公司 | 用于二异丁烯的Pd-催化的羟基羰基化的方法:乙酸/二异丁烯比例 |
CN109942402A (zh) * | 2017-12-21 | 2019-06-28 | 赢创德固赛有限公司 | 二异丁烯的经Pd催化的羟基羰基化方法:溶剂的影响 |
CN109942403A (zh) * | 2017-12-21 | 2019-06-28 | 赢创德固赛有限公司 | 二异丁烯的经Pd催化的羟基羰基化方法:硫酸/配体比率 |
CN109942400A (zh) * | 2017-12-21 | 2019-06-28 | 赢创德固赛有限公司 | 二异丁烯的经Pd催化的羟基羰基化方法:3,5,5-三甲基己酸/H2O的比率 |
CN109942405A (zh) * | 2017-12-21 | 2019-06-28 | 赢创德固赛有限公司 | 二异丁烯的经Pd催化的羟基羰基化方法:配体/Pd比率 |
CN109942401A (zh) * | 2017-12-21 | 2019-06-28 | 赢创德固赛有限公司 | 将烯烃直接转化为羧酸的方法 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2448368A (en) * | 1945-11-19 | 1948-08-31 | Du Pont | Organic acid synthesis |
US2768968A (en) * | 1953-06-13 | 1956-10-30 | Basf Ag | Carbonylation of olefins with cobalt or nickel complex catalysts |
US2854458A (en) * | 1954-07-15 | 1958-09-30 | Basf Ag | Complex heavy metal salts |
US2911422A (en) * | 1955-05-28 | 1959-11-03 | L Ind Mineraria E Chimica Soc | Synthesis of carboxylic acids from olefinic compounds, carbon monoxide and water in the presence of a solvent |
US2916513A (en) * | 1956-07-05 | 1959-12-08 | Basf Ag | Production of acrylic acid and its esters |
US3023237A (en) * | 1953-02-17 | 1962-02-27 | Basf Ag | Process for producing acrylic acid |
US3481975A (en) * | 1965-01-27 | 1969-12-02 | V N | Method of preparing dicarboxylic acids |
GB1281615A (en) * | 1970-02-23 | 1972-07-12 | Ici Ltd | Production of methyl esters |
US3906016A (en) * | 1971-12-28 | 1975-09-16 | Lion Fat Oil Co Ltd | Method of preparing esters of carboxylic acids |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE927090C (de) * | 1953-06-14 | 1955-04-28 | Basf Ag | Verfahren zur Herstellung von Carbonsaeuren und deren funktionellen Derivaten |
FR2047717A5 (en) * | 1969-05-14 | 1971-03-12 | Ici Ltd | Esters from olefins using metal carbonyl - catalysts |
-
1977
- 1977-03-04 DE DE2709438A patent/DE2709438C3/de not_active Expired
-
1978
- 1978-02-01 US US05/874,316 patent/US4619790A/en not_active Expired - Lifetime
- 1978-02-23 BE BE185433A patent/BE864265A/fr not_active IP Right Cessation
- 1978-03-01 JP JP53022175A patent/JPS6058900B2/ja not_active Expired
- 1978-03-03 AT AT154178A patent/AT356641B/de not_active IP Right Cessation
- 1978-03-03 FR FR7806146A patent/FR2382425A1/fr active Granted
- 1978-03-03 GB GB8500/78A patent/GB1595037A/en not_active Expired
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2448368A (en) * | 1945-11-19 | 1948-08-31 | Du Pont | Organic acid synthesis |
US3023237A (en) * | 1953-02-17 | 1962-02-27 | Basf Ag | Process for producing acrylic acid |
US2768968A (en) * | 1953-06-13 | 1956-10-30 | Basf Ag | Carbonylation of olefins with cobalt or nickel complex catalysts |
US2854458A (en) * | 1954-07-15 | 1958-09-30 | Basf Ag | Complex heavy metal salts |
US2911422A (en) * | 1955-05-28 | 1959-11-03 | L Ind Mineraria E Chimica Soc | Synthesis of carboxylic acids from olefinic compounds, carbon monoxide and water in the presence of a solvent |
US2916513A (en) * | 1956-07-05 | 1959-12-08 | Basf Ag | Production of acrylic acid and its esters |
US3481975A (en) * | 1965-01-27 | 1969-12-02 | V N | Method of preparing dicarboxylic acids |
GB1281615A (en) * | 1970-02-23 | 1972-07-12 | Ici Ltd | Production of methyl esters |
US3906016A (en) * | 1971-12-28 | 1975-09-16 | Lion Fat Oil Co Ltd | Method of preparing esters of carboxylic acids |
Cited By (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4665213A (en) * | 1985-08-29 | 1987-05-12 | The British Petroleum Company P.L.C. | Process for the production of esters |
US20040238785A1 (en) * | 2000-12-22 | 2004-12-02 | Eddy Van Driessche | Ester-containing fluid compositions |
US7582226B2 (en) | 2000-12-22 | 2009-09-01 | Exxonmobil Chemical Patents Inc. | Ester-containing fluid compositions |
KR100763216B1 (ko) | 2001-02-13 | 2007-10-08 | 옥세노 올레핀케미 게엠베하 | 고순도 디이소부텐의 제조방법 |
KR20190075834A (ko) * | 2017-12-21 | 2019-07-01 | 에보니크 데구사 게엠베하 | 디이소부텐의 Pd-촉매된 히드록시카르보닐화 방법: 황산/리간드 비 |
KR20190075842A (ko) * | 2017-12-21 | 2019-07-01 | 에보니크 데구사 게엠베하 | 디이소부텐의 Pd-촉매된 히드록시카르보닐화 방법: 용매의 효과 |
CN109942402A (zh) * | 2017-12-21 | 2019-06-28 | 赢创德固赛有限公司 | 二异丁烯的经Pd催化的羟基羰基化方法:溶剂的影响 |
CN109942403A (zh) * | 2017-12-21 | 2019-06-28 | 赢创德固赛有限公司 | 二异丁烯的经Pd催化的羟基羰基化方法:硫酸/配体比率 |
CN109942400A (zh) * | 2017-12-21 | 2019-06-28 | 赢创德固赛有限公司 | 二异丁烯的经Pd催化的羟基羰基化方法:3,5,5-三甲基己酸/H2O的比率 |
CN109942405A (zh) * | 2017-12-21 | 2019-06-28 | 赢创德固赛有限公司 | 二异丁烯的经Pd催化的羟基羰基化方法:配体/Pd比率 |
CN109942401A (zh) * | 2017-12-21 | 2019-06-28 | 赢创德固赛有限公司 | 将烯烃直接转化为羧酸的方法 |
KR20190075840A (ko) * | 2017-12-21 | 2019-07-01 | 에보니크 데구사 게엠베하 | 디이소부텐을 카르복실산으로 직접 전환시키는 방법 |
KR20190075836A (ko) * | 2017-12-21 | 2019-07-01 | 에보니크 데구사 게엠베하 | 디이소부텐의 Pd-촉매된 히드록시카르보닐화 방법: 아세트산/디이소부텐 비 |
KR20190075841A (ko) * | 2017-12-21 | 2019-07-01 | 에보니크 데구사 게엠베하 | 알켄을 카르복실산으로 직접 전환시키는 방법 |
KR20190075839A (ko) * | 2017-12-21 | 2019-07-01 | 에보니크 데구사 게엠베하 | 디이소부텐의 Pd-촉매된 히드록시카르보닐화 방법: 3,5,5-트리메틸헥산산/H₂O의 비 |
KR20190075835A (ko) * | 2017-12-21 | 2019-07-01 | 에보니크 데구사 게엠베하 | 디이소부텐의 Pd-촉매된 히드록시카르보닐화 방법: 리간드/Pd 비 |
CN109942399A (zh) * | 2017-12-21 | 2019-06-28 | 赢创德固赛有限公司 | 将二异丁烯直接转化为羧酸的方法 |
CN109942398A (zh) * | 2017-12-21 | 2019-06-28 | 赢创德固赛有限公司 | 用于二异丁烯的Pd-催化的羟基羰基化的方法:乙酸/二异丁烯比例 |
KR102144331B1 (ko) | 2017-12-21 | 2020-08-13 | 에보니크 오퍼레이션즈 게엠베하 | 알켄을 카르복실산으로 직접 전환시키는 방법 |
KR102144335B1 (ko) | 2017-12-21 | 2020-08-13 | 에보니크 오퍼레이션즈 게엠베하 | 디이소부텐의 Pd-촉매된 히드록시카르보닐화 방법: 용매의 효과 |
KR102145214B1 (ko) | 2017-12-21 | 2020-08-18 | 에보니크 오퍼레이션즈 게엠베하 | 디이소부텐의 Pd-촉매된 히드록시카르보닐화 방법: 아세트산/디이소부텐 비 |
KR102145213B1 (ko) | 2017-12-21 | 2020-08-18 | 에보니크 오퍼레이션즈 게엠베하 | 디이소부텐의 Pd-촉매된 히드록시카르보닐화 방법: 황산/리간드 비 |
KR102146328B1 (ko) | 2017-12-21 | 2020-08-21 | 에보니크 오퍼레이션즈 게엠베하 | 디이소부텐의 Pd-촉매된 히드록시카르보닐화 방법: 리간드/Pd 비 |
KR102147735B1 (ko) | 2017-12-21 | 2020-08-25 | 에보니크 오퍼레이션즈 게엠베하 | 디이소부텐을 카르복실산으로 직접 전환시키는 방법 |
KR102148186B1 (ko) | 2017-12-21 | 2020-08-26 | 에보니크 오퍼레이션즈 게엠베하 | 디이소부텐의 Pd-촉매된 히드록시카르보닐화 방법: 3,5,5-트리메틸헥산산/H₂O의 비 |
CN109942403B (zh) * | 2017-12-21 | 2021-08-31 | 赢创运营有限公司 | 二异丁烯的经Pd催化的羟基羰基化方法:硫酸/配体比率 |
CN109942405B (zh) * | 2017-12-21 | 2021-09-17 | 赢创运营有限公司 | 二异丁烯的经Pd催化的羟基羰基化方法:配体/Pd比率 |
CN109942401B (zh) * | 2017-12-21 | 2021-09-24 | 赢创运营有限公司 | 将烯烃直接转化为羧酸的方法 |
CN109942400B (zh) * | 2017-12-21 | 2021-10-15 | 赢创运营有限公司 | 二异丁烯的经Pd催化的羟基羰基化方法:3,5,5-三甲基己酸/H2O的比率 |
CN109942399B (zh) * | 2017-12-21 | 2021-11-30 | 赢创运营有限公司 | 将二异丁烯直接转化为羧酸的方法 |
CN109942398B (zh) * | 2017-12-21 | 2022-09-20 | 赢创运营有限公司 | 用于二异丁烯的Pd-催化的羟基羰基化的方法:乙酸/二异丁烯比例 |
TWI779141B (zh) * | 2017-12-21 | 2022-10-01 | 德商贏創運營有限公司 | 在硫酸/配位體比率下進行二異丁烯之鈀催化羥基羰基化的方法 |
Also Published As
Publication number | Publication date |
---|---|
JPS6058900B2 (ja) | 1985-12-23 |
GB1595037A (en) | 1981-08-05 |
JPS53111008A (en) | 1978-09-28 |
DE2709438A1 (de) | 1978-09-07 |
DE2709438C3 (de) | 1980-01-17 |
DE2709438B2 (de) | 1979-05-23 |
FR2382425A1 (fr) | 1978-09-29 |
ATA154178A (de) | 1979-10-15 |
BE864265A (fr) | 1978-08-23 |
AT356641B (de) | 1980-05-12 |
FR2382425B1 (fr) | 1983-09-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6800783B2 (en) | Method for the synthesis of aliphatic carboxylic acids from aldehydes | |
US4619790A (en) | Manufacture of higher alkylcarboxylic acids | |
KR100213514B1 (ko) | 카르복실산 무수물의 제조방법 | |
GB1565716A (en) | Manufacture of alkylcarboxylic acids | |
US3660493A (en) | Hydroformylation process | |
JP2761603B2 (ja) | 3―ペンテン酸の製造法 | |
US4360692A (en) | Preparation of formylvalerates | |
JPS5984838A (ja) | カルボン酸の製造方法 | |
CA1146970A (fr) | Methode de preparation d'acides aliphatiques carboxyliques | |
US3912785A (en) | Oxo-related reaction making triethanolmethane and 3-methylpentanediol-1,5 from hexenediols | |
US4614816A (en) | Preparation of carboxylic acids and esters thereof | |
US2600571A (en) | Butadiene-cobalt carbonyl hydride adduct | |
JPS60208945A (ja) | 第2のエステルの製造方法 | |
JPS5984840A (ja) | カルボン酸の製造方法 | |
CA1048534A (fr) | Esters allyliques d'acides carboxyliques et d'alcools allyliques | |
EP0428979B1 (fr) | Procédé de carbonylation des butènols allyliques et des esters butènoliques | |
US4310686A (en) | Preparation of butanedicarboxylic esters | |
US2710879A (en) | Synthesis of carboxylic acids | |
US3947458A (en) | Preparation of amines | |
US4096188A (en) | Preparation of straight chain aldehydes | |
DE68920562T2 (de) | Isomerisierung von Carbonsäuren. | |
EP0047831B1 (fr) | Procédé de préparation d'esters, surtout linéaires, d'acides carboxyliques aliphatiques | |
US3917677A (en) | Production of carboxylic acid esters by hydroesterification | |
US4414421A (en) | Process for the preparation of glycol aldehyde | |
US4460510A (en) | Process for alkoxycarbonylating alpha-olefins having a single branch |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |